CA2489243C - Process for the preparation of expandable vinylaromatic polymers - Google Patents
Process for the preparation of expandable vinylaromatic polymers Download PDFInfo
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- CA2489243C CA2489243C CA2489243A CA2489243A CA2489243C CA 2489243 C CA2489243 C CA 2489243C CA 2489243 A CA2489243 A CA 2489243A CA 2489243 A CA2489243 A CA 2489243A CA 2489243 C CA2489243 C CA 2489243C
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- beads
- process according
- expandable
- ranging
- previous
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- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011324 bead Substances 0.000 claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000000375 suspending agent Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- -1 chlo-rine or bromine Chemical class 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000001298 alcohols Chemical group 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 235000017168 chlorine Nutrition 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229940060038 chlorine Drugs 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- 239000006260 foam Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 235000019731 tricalcium phosphate Nutrition 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 3
- 229940078499 tricalcium phosphate Drugs 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 229940057948 magnesium stearate Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940102838 methylmethacrylate Drugs 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- WGZYQOSEVSXDNI-UHFFFAOYSA-N 1,1,2-trifluoroethane Chemical compound FCC(F)F WGZYQOSEVSXDNI-UHFFFAOYSA-N 0.000 description 1
- SVHAMPNLOLKSFU-UHFFFAOYSA-N 1,2,2-trichloroethenylbenzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC=C1 SVHAMPNLOLKSFU-UHFFFAOYSA-N 0.000 description 1
- AUHKVLIZXLBQSR-UHFFFAOYSA-N 1,2-dichloro-3-(1,2,2-trichloroethenyl)benzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC(Cl)=C1Cl AUHKVLIZXLBQSR-UHFFFAOYSA-N 0.000 description 1
- XPXMCUKPGZUFGR-UHFFFAOYSA-N 1-chloro-2-(1,2,2-trichloroethenyl)benzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC=C1Cl XPXMCUKPGZUFGR-UHFFFAOYSA-N 0.000 description 1
- FJSRPVWDOJSWBX-UHFFFAOYSA-N 1-chloro-4-[1-(4-chlorophenyl)-2,2,2-trifluoroethyl]benzene Chemical compound C=1C=C(Cl)C=CC=1C(C(F)(F)F)C1=CC=C(Cl)C=C1 FJSRPVWDOJSWBX-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- FMFHUEMLVAIBFI-UHFFFAOYSA-N 2-phenylethenyl acetate Chemical compound CC(=O)OC=CC1=CC=CC=C1 FMFHUEMLVAIBFI-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920013701 VORANOL™ Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229940116441 divinylbenzene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Process for the preparation of expandable vinylaromatic polymers which comprises: a) polymerizing in aqueous suspension at last one vinylaromatic monomer in the presence of a suspending agent selected from inorganic salts of phosphoric acid; b) recovering the expandable beads from the reaction container; c) washing the beads thus obtained with an aqueous solution containing 0.005-2% by weight of a non-ionic surface-active agent; d) recovering the washed beads substantially without any inorganic salt of phosphoric acid, on the surface, and drying them in a stream of air.
Description
PROCESS FOR THE PREPARATION OF EXPANDABLE VINYLAROMATIC
POLYMERS
The present invention relates to a process for the preparation of expandable vinylaromatic polymers.
More specifically, the present invention relates to a process for the preparation of expandable polystyrene.
Vinylaromatic polymers, and among these, polystyrene in particular, are known products which have been adopted for a long time for preparing compact and/or expanded arti-cles which can be used in various applicative sectors, among which the most important are household appliances, the transport and building industries, office machines, etc. A particularly interesting sector is the field of thermal insulation, where vinylaromatic polymers are essen-tially used in expanded form.
These expanded products are obtained by swelling, in a pre-expander, beads of expandable polymer previously im-pregnated with an expanding agent and molding the swollen particles inside a closed mould by means of the contempora-neous effect of pressure and temperature. The swelling of the particles is generally effected with vapour, or another gas, maintained at a temperature slightly higher than the glass transition temperature (Tg) of the polymer.
In the preparation of expandable particles, treatment such as washing and drying at the end of the polymerization to remove any chemicals possibly present on the surface of the particles, is also known. In particular, expandable beads obtained by means of a process in aqueous suspension can be treated at the end of the polymerization to elimi-nate the presence of the suspending agent which "fouls" the surface of the particles, creating drawbacks. The presence of the suspending agent, in fact, leads to long drying times and also to a poor processability (for example lim-ited adhesion in the moulding phase) during the preparation of the expanded products.
The drying, generally carried out in warm air, re-quires long times, as it must be effected at low tempera-tures, lower than 40°C, to avoid losses of expanding agent.
In patent U.S. 5,041,465, the polymerization of the particles is carried out with a finely divided calcium phosphate (TCP) as suspending agent: the removal of the TCP
is effected with a treatment washing by acid products, in particular with hydrochloric acid.
Also in patent U.S. 4,793,406, the removal of the in-organic suspending agent is carried out with strong acids.
U.S. patent 4,286,069 also describes a process for the preparation in aqueous suspension of expandable beads of styrene polymers in which, when the suspending agent is an inorganic salt of phosphoric acid, for example tricalcium phosphate, the beads obtained at the end of the polymeriza-tion are washed with nitric acid.
In these cases, the drying times are brief but the use of strong acids creates serious problems for the safety of operators and plants, with considerable additional costs in the production of expandable beads.
In order to overcome the disadvantages associated with treatment/washings with acids, the use of organic suspend-ing agents has been proposed. In patent U.S. 4,560,705, for example, inorganic suspending agents are not used, thus avoiding the use of acids for washing the particles. The drying is carried out in short times but although the sus-pending agent, for example sodium dodecylbenzenesulfonate, does not require a washing phase, it produces foam in the wastewater.
The presence of foam in the wastewater makes it neces-sary to have a specific separation plant or causes serious problems in the biological plants as the active sludge can be dragged away by the foam without decomposing the organic residues.
POLYMERS
The present invention relates to a process for the preparation of expandable vinylaromatic polymers.
More specifically, the present invention relates to a process for the preparation of expandable polystyrene.
Vinylaromatic polymers, and among these, polystyrene in particular, are known products which have been adopted for a long time for preparing compact and/or expanded arti-cles which can be used in various applicative sectors, among which the most important are household appliances, the transport and building industries, office machines, etc. A particularly interesting sector is the field of thermal insulation, where vinylaromatic polymers are essen-tially used in expanded form.
These expanded products are obtained by swelling, in a pre-expander, beads of expandable polymer previously im-pregnated with an expanding agent and molding the swollen particles inside a closed mould by means of the contempora-neous effect of pressure and temperature. The swelling of the particles is generally effected with vapour, or another gas, maintained at a temperature slightly higher than the glass transition temperature (Tg) of the polymer.
In the preparation of expandable particles, treatment such as washing and drying at the end of the polymerization to remove any chemicals possibly present on the surface of the particles, is also known. In particular, expandable beads obtained by means of a process in aqueous suspension can be treated at the end of the polymerization to elimi-nate the presence of the suspending agent which "fouls" the surface of the particles, creating drawbacks. The presence of the suspending agent, in fact, leads to long drying times and also to a poor processability (for example lim-ited adhesion in the moulding phase) during the preparation of the expanded products.
The drying, generally carried out in warm air, re-quires long times, as it must be effected at low tempera-tures, lower than 40°C, to avoid losses of expanding agent.
In patent U.S. 5,041,465, the polymerization of the particles is carried out with a finely divided calcium phosphate (TCP) as suspending agent: the removal of the TCP
is effected with a treatment washing by acid products, in particular with hydrochloric acid.
Also in patent U.S. 4,793,406, the removal of the in-organic suspending agent is carried out with strong acids.
U.S. patent 4,286,069 also describes a process for the preparation in aqueous suspension of expandable beads of styrene polymers in which, when the suspending agent is an inorganic salt of phosphoric acid, for example tricalcium phosphate, the beads obtained at the end of the polymeriza-tion are washed with nitric acid.
In these cases, the drying times are brief but the use of strong acids creates serious problems for the safety of operators and plants, with considerable additional costs in the production of expandable beads.
In order to overcome the disadvantages associated with treatment/washings with acids, the use of organic suspend-ing agents has been proposed. In patent U.S. 4,560,705, for example, inorganic suspending agents are not used, thus avoiding the use of acids for washing the particles. The drying is carried out in short times but although the sus-pending agent, for example sodium dodecylbenzenesulfonate, does not require a washing phase, it produces foam in the wastewater.
The presence of foam in the wastewater makes it neces-sary to have a specific separation plant or causes serious problems in the biological plants as the active sludge can be dragged away by the foam without decomposing the organic residues.
The drawbacks associated with these two systems of treating expandable beads are evident. In the former case, the treatment with acids requires the use of technological expedients which influence the production costs, in the latter case, the presence of foam makes any treatment of the wastewater with normal biological plants, difficult.
The Applicant has now found a system for guaranteeing a short drying time of the expandable beads of vinylaro-matic polymers obtained in aqueous suspension with inor-ganic salts of phosphoric acid, for example tricalcium phosphate or magnesium phosphate, without coming up against the disadvantages observed in the state of the art. These salts can be added to the polymerization mixture either al-ready finely subdivided or synthesized in situ by the reac-tion, for example, between sodium pyrophosphate and magne-slum sulfate.
An object of the present invention therefore relates to a process for the preparation of expandable vinylaro-matic polymers which comprises:
a) polymerizing in aqueous suspension at least one vi-nylaromatic monomer in the presence of a suspending agent selected from inorganic salts of phosphoric acid;
b) recovering the expandable beads from the reaction con-tainer;
c) washing the beads thus obtained with an aqueous solu-tion containing 0.005-2o by weight of a non-ionic sur-face-active agent;
d) recovering the washed beads substantially without any inorganic salt of phosphoric acid, on the surface, and drying them in a stream of air.
According to the present invention, the polymerization process in aqueous suspension of the vinylaromatic monomer is carried out under the conditions and in the presence of additives, together with the suspending agent, well known in the art. For example, the polymerization can be carried out in the presence of an initiator system and an expanding system. The initiator system comprises two peroxides, one with a half time of an hour at 85°-95°C and the other with a half time of an hour at 110-120°C.
Any expanding agent capable of being englobed in the polymeric matrix can be used in a combination with the vi-nylaromatic polymers object of the present invention. In general, liquid substances are used, with a boiling point ranging from 10 to 100°C, preferably from 20 to 80°C. Typi-cal examples are aliphatic hydrocarbons, freon, carbon di-oxide, water, etc.
The expanding agent can be added to the polymer during the polymerization phase, or, alternatively, by impregna-tion of the beads produced at the end of the polymerization or by injection into the molten product. At the end of the addition, a polymer is obtained in the form of beads, which can be transformed to produce expanded articles with a den-sity ranging from 5 to 50 g/l, preferably from 8 to 25 g/l, with an excellent thermal insulation capacity. In order to favour the retention of the expanding agent in the poly-merit matrix, additives capable of forming bonds both of the weak type (for example hydrogen bridges) or strong type (for example acid-base adducts) can be used with the ex-panding agent. Examples of these additives are methyl alco-hol, isopropyl alcohol, dioctylphthalate, dimethylcarbon-ate, compounds containing an amine group. These additives are generally added during the polymerization and/or enbod-ied in the polymer together with the expanding agent.
The expanding agents are preferably added during the polymerization phase and are selected from: aliphatic or cycloaliphatic hydrocarbons containing from 3 to 6 carbon atoms, such as n-pentane, iso-pentane, cyclopentane or their mixtures; halogenated derivatives of aliphatic hydro-carbons containing from 1 to 3 carbon atoms such as, for example, dichlorodifluoromethane, 1,2,2-trifluoroethane, 1,1,2-trifluoroethane; carbon dioxide and water.
The term "vinylaromatic monomer~~, as used in the pres ent description and claims, essentially refers to a product which corresponds to the following general formula:
The Applicant has now found a system for guaranteeing a short drying time of the expandable beads of vinylaro-matic polymers obtained in aqueous suspension with inor-ganic salts of phosphoric acid, for example tricalcium phosphate or magnesium phosphate, without coming up against the disadvantages observed in the state of the art. These salts can be added to the polymerization mixture either al-ready finely subdivided or synthesized in situ by the reac-tion, for example, between sodium pyrophosphate and magne-slum sulfate.
An object of the present invention therefore relates to a process for the preparation of expandable vinylaro-matic polymers which comprises:
a) polymerizing in aqueous suspension at least one vi-nylaromatic monomer in the presence of a suspending agent selected from inorganic salts of phosphoric acid;
b) recovering the expandable beads from the reaction con-tainer;
c) washing the beads thus obtained with an aqueous solu-tion containing 0.005-2o by weight of a non-ionic sur-face-active agent;
d) recovering the washed beads substantially without any inorganic salt of phosphoric acid, on the surface, and drying them in a stream of air.
According to the present invention, the polymerization process in aqueous suspension of the vinylaromatic monomer is carried out under the conditions and in the presence of additives, together with the suspending agent, well known in the art. For example, the polymerization can be carried out in the presence of an initiator system and an expanding system. The initiator system comprises two peroxides, one with a half time of an hour at 85°-95°C and the other with a half time of an hour at 110-120°C.
Any expanding agent capable of being englobed in the polymeric matrix can be used in a combination with the vi-nylaromatic polymers object of the present invention. In general, liquid substances are used, with a boiling point ranging from 10 to 100°C, preferably from 20 to 80°C. Typi-cal examples are aliphatic hydrocarbons, freon, carbon di-oxide, water, etc.
The expanding agent can be added to the polymer during the polymerization phase, or, alternatively, by impregna-tion of the beads produced at the end of the polymerization or by injection into the molten product. At the end of the addition, a polymer is obtained in the form of beads, which can be transformed to produce expanded articles with a den-sity ranging from 5 to 50 g/l, preferably from 8 to 25 g/l, with an excellent thermal insulation capacity. In order to favour the retention of the expanding agent in the poly-merit matrix, additives capable of forming bonds both of the weak type (for example hydrogen bridges) or strong type (for example acid-base adducts) can be used with the ex-panding agent. Examples of these additives are methyl alco-hol, isopropyl alcohol, dioctylphthalate, dimethylcarbon-ate, compounds containing an amine group. These additives are generally added during the polymerization and/or enbod-ied in the polymer together with the expanding agent.
The expanding agents are preferably added during the polymerization phase and are selected from: aliphatic or cycloaliphatic hydrocarbons containing from 3 to 6 carbon atoms, such as n-pentane, iso-pentane, cyclopentane or their mixtures; halogenated derivatives of aliphatic hydro-carbons containing from 1 to 3 carbon atoms such as, for example, dichlorodifluoromethane, 1,2,2-trifluoroethane, 1,1,2-trifluoroethane; carbon dioxide and water.
The term "vinylaromatic monomer~~, as used in the pres ent description and claims, essentially refers to a product which corresponds to the following general formula:
CR=CH2 (I) ~n wherein n is zero or an integer ranging from 1 to 5, R is a hydrogen atom or a methyl and Y is a halogen, such as chlo-rine or bromine, or an alkyl or alkoxyl radical having from 1 to 4 carbon atoms.
Examples of vinylaromatic monomers having the general formula defined above are: styrene, a-methylstyrene, meth-ylstyrene, ethylstyrene, butylstyrene, dimethylstyrene, mono-, di-, tri-, tetra- and penta-chlorostyrene, bromo-styrene, methoxy-styrene, acetoxy-styrene, etc. Styrene and a-methylstyrene are the preferred vinylaromatic monomers.
The vinylaromatic monomers having general formula (I) can be used alone or in a mixture of up to 50% by weight with other copolymerizable monomers. Examples of these monomers are (meth)acrylic acid, C1-C4 alkyl esters of (meth)acrylic acid, such as methyl acrylate, methyl-methacrylate, ethyl acrylate, ethylmethacrylate, isopropyl acrylate, butyl acrylate, amides and nitriles of (meth)acrylic acid such as acrylamide, methacrylamide, ac-rylonitrile, methacrylonitrile, butadiene, ethylene, divi-nylbenzene, malefic anhydride, etc. Preferred copolymeri-table monomers are acrylonitrile and methylmethacrylate.
-The vinylaromatic polymer or copolymer which is ob-tained has a molecular weight Mw ranging from 50,000 to 250,000, preferably from 70,000 to 200,000. In general, greater details on a process for the preparation of expand-able vinylaromatic polymers in aqueous solution or, more generally, on polymerization in suspension, can be found in Journal of Macromolecular Science, Review in Macromolecular Chemistry and Physics~c31 (263) 215-299 (1991) or in inter-national patent application WO 98/51734.
Conventional additives, generally used with commercial materials, such as pigments, stabilizers, flame-retardant agents, mineral fillers of athermanous materials, anti-static agents, detaching agents, shock-resistant agents, etc., can be added to the expandable vinylaromatic polymers obtained with the process, object of the present invention.
In particular, it is preferable to add during the polymeri-ration mineral fillers of athermanous materials, such as graphite or refracting materials such as titanium dioxide, in a quantity ranging from 0.05 to 25% by weight, calcu-lated with respect to the resulting polymer.
At the end of the polymerization, substantially spherical polymer beads are obtained, with an average di-ameter ranging from 0.2 to 2 mm, inside which the expanding agent is homogeneously dispersed.
To improve the stability of the suspension, it is pos-- g _ Bible to increase the viscosity of the reagent solution by dissolving the vinylaromatic polymer therein, in a concen-tration ranging from 1 to 30% by weight, preferably from 5 to 20%, calculated with respect to the monomer alone. The solution can be obtained either by dissolving a preformed polymer (for example fresh polymer or the waste products of previous polymerizations and/or expansions) in the reagent mixture or by pre-polymerizing the monomer, or mixture of monomers, in mass, in order to obtain the above concentra-tions, and then continuing the polymerization in aqueous suspension in the presence of the remaining additives.
At the end of the polymerization, the beads are dis-charged from the polymerization reactor and washed, in con-tinuous or batchwise, with a solution containing the sur-face-active agent. The non-ionic surface-active agent is selected from alcohols/Cg-C1$ ethoxylated and/or propoxy-lated fatty acids (Empilan KCL, KCX of Huntsmann) , ethoxy-lated and/or propoxylated glycerin ethers with an average molecular weight Mw ranging from 3500 to 5000 (Voranol 4555 of Dow), glycols condensed with ethylene oxide and/or pro-pylene oxide, ethoxylated and/or propoxylated nonyl phenols with 0-5 units of ethylene oxide and/or propylene oxide (Empilan NP of Huntsmann), ethoxylated and/or propoxylated sorbitol with 5-20 units of ethylene oxide and/or propylene oxide (for example Armotan PN020 of ICI), fatty acids of coconut salified with K, MEA (Nansa of Huntsmann).
The main types of these surface-active agents are de-scribed in "Dispersing Powders in Liquids", Ralph D., Nel-son Jr., Ed. Elsevier, 1988.
The washing generally takes place at a temperature ranging from 20 to 50°C, in stirred containers containing the surface-active agent in a concentration ranging from 0.01 to 2% by weight, preferably from 0.02 to 1%.
At the end of the polymerization and washing with the surface-active agent, the beads produced are subjected to pre-treatment generally applied to traditional materials and which essentially consists in:
1. coating the beads with a liquid antistatic agent such as amines, tertiary ethoxylated alkylamines, ethylene ox-L5 ide-propylene oxide copolymers, etc. The purpose of this agent is to facilitate both the adhesion of the coating and also the screening of the beads prepared in suspen-sion;
2. applying the coating to the above beads, said coating essentially consisting of a mixture of mono-, di- and tri-esters of glycerin (or other alcohols) with fatty acids and of metallic stearates such as zinc and/or mag-nesium stearate.
Some illustrative but non-limiting examples are pro-?5 vided for a better understanding of the present invention and for its embodiment.
100 parts of styrene monomer, 0.30 parts of benzoyl peroxide, 0.15 parts of terbutylperbenzoate, 100 parts of demineralized water, 0.2 parts of tricalcium phosphate and 20 ppm of sodium dodecylbenzenesulfonate, were charged into a 2 litre reactor equipped with a stirrer.
The mixture was then heated to 90°C for 4 hours and to 125°C for a further 6 hours.
The expanding agent (7 parts of n-pentane) was added during the rise from 90 to 125°C.
At the end of the polymerization, the beads were cen-trifuged and subsequently washed with an equal part of de-mineralized water.
The beads were then centrifuged and placed in a column having a diameter of 10 cm and a height of 80 cm for drying with air at 23°C (flow-rate - 3, 000 1/h) . The time neces-sary for the drying was 40'.
0 . 02 0 of ethoxylated amine was added to the beads of expandable polymer thus produced, which were then sieved, separating the fraction with a diameter ranging from 1 to 1.5 mm.
0.250 of glycerylmonostearate and 0.05% of magnesium stearate were then added to the fraction.
The product is pre-expanded with vapour at a tempera-ture of 100°C at a density of 15 g/1 and then aged for a day.
The expanded beads were used the following day for the moulding of blocks (dimensions 1040 x 1030 x 550 mm) at a pressure of 0.5 bars, measuring the cooling time (which proved to be 12 minutes).
The blocks were then cut to prepare flat sheets on which the sintering was measured, which proved to be equal to 150.
50 g of the mother liquor of the polymerization and washing were put into a 200 g phial and stirred for a min-ute to evaluate the presence of foam. The formation of foam 1 cm high was observed, which completely disappeared after resting for 10 minutes.
The beads polymerized according to Comparative example 1 were centrifuged and then washed with an equal part of demineralized water containing 0.050 of sodium dodecylben-zenesulfonate.
The beads were then centrifuged and placed in a column having a diameter of 10 cm and a height of 80 cm for drying with air at 23°C (flow-rate - 3, 000 1/h) . The time neces-sary for the drying was 11 minutes.
The additive was added to the beads thus produced, which were sieved, expanded at 15 g/1, moulded according to the same procedure adopted in comparative example 1.
The cooling time proved to be 11 minutes whereas the sintering was equal to 50%.
50 g of the mother liquor of the polymerization and washing were put into a 200 g phial and stirred for a min ute to evaluate the presence of foam. The formation of per sistent foam, 10 cm high, was observed. The height of the foam was still 6 cm after resting for 10 minutes.
rmTw~nr ~
The beads polymerized according to Comparative example 1 were centrifuged and then washed with an equal part of demineralized water containing 0.05% of a non-ionic sur-face-active agent consisting of fatty alcohol condensed with ethylene oxide and propylene oxide, sold by Huntsman under the trade-name of Empilan 2638.
The beads were then centrifuged and placed in a column having a diameter of 10 cm and a height of 80 cm for drying with air at 23°C (flow-rate - 3,000 1/h). The time neces-sary for the drying was 10 minutes.
The additive was added to the beads thus prepared, which were sieved, etc., using the same procedure adopted in Comparative example l: the cooling time of the block proved to be 10 minutes whereas the sintering was equal to 50%.
50 g of the mother liquor of the polymerization and washing were put into a 200 g phial and stirred for a min-ute to evaluate the presence of foam. In this case no foam was present.
Examples of vinylaromatic monomers having the general formula defined above are: styrene, a-methylstyrene, meth-ylstyrene, ethylstyrene, butylstyrene, dimethylstyrene, mono-, di-, tri-, tetra- and penta-chlorostyrene, bromo-styrene, methoxy-styrene, acetoxy-styrene, etc. Styrene and a-methylstyrene are the preferred vinylaromatic monomers.
The vinylaromatic monomers having general formula (I) can be used alone or in a mixture of up to 50% by weight with other copolymerizable monomers. Examples of these monomers are (meth)acrylic acid, C1-C4 alkyl esters of (meth)acrylic acid, such as methyl acrylate, methyl-methacrylate, ethyl acrylate, ethylmethacrylate, isopropyl acrylate, butyl acrylate, amides and nitriles of (meth)acrylic acid such as acrylamide, methacrylamide, ac-rylonitrile, methacrylonitrile, butadiene, ethylene, divi-nylbenzene, malefic anhydride, etc. Preferred copolymeri-table monomers are acrylonitrile and methylmethacrylate.
-The vinylaromatic polymer or copolymer which is ob-tained has a molecular weight Mw ranging from 50,000 to 250,000, preferably from 70,000 to 200,000. In general, greater details on a process for the preparation of expand-able vinylaromatic polymers in aqueous solution or, more generally, on polymerization in suspension, can be found in Journal of Macromolecular Science, Review in Macromolecular Chemistry and Physics~c31 (263) 215-299 (1991) or in inter-national patent application WO 98/51734.
Conventional additives, generally used with commercial materials, such as pigments, stabilizers, flame-retardant agents, mineral fillers of athermanous materials, anti-static agents, detaching agents, shock-resistant agents, etc., can be added to the expandable vinylaromatic polymers obtained with the process, object of the present invention.
In particular, it is preferable to add during the polymeri-ration mineral fillers of athermanous materials, such as graphite or refracting materials such as titanium dioxide, in a quantity ranging from 0.05 to 25% by weight, calcu-lated with respect to the resulting polymer.
At the end of the polymerization, substantially spherical polymer beads are obtained, with an average di-ameter ranging from 0.2 to 2 mm, inside which the expanding agent is homogeneously dispersed.
To improve the stability of the suspension, it is pos-- g _ Bible to increase the viscosity of the reagent solution by dissolving the vinylaromatic polymer therein, in a concen-tration ranging from 1 to 30% by weight, preferably from 5 to 20%, calculated with respect to the monomer alone. The solution can be obtained either by dissolving a preformed polymer (for example fresh polymer or the waste products of previous polymerizations and/or expansions) in the reagent mixture or by pre-polymerizing the monomer, or mixture of monomers, in mass, in order to obtain the above concentra-tions, and then continuing the polymerization in aqueous suspension in the presence of the remaining additives.
At the end of the polymerization, the beads are dis-charged from the polymerization reactor and washed, in con-tinuous or batchwise, with a solution containing the sur-face-active agent. The non-ionic surface-active agent is selected from alcohols/Cg-C1$ ethoxylated and/or propoxy-lated fatty acids (Empilan KCL, KCX of Huntsmann) , ethoxy-lated and/or propoxylated glycerin ethers with an average molecular weight Mw ranging from 3500 to 5000 (Voranol 4555 of Dow), glycols condensed with ethylene oxide and/or pro-pylene oxide, ethoxylated and/or propoxylated nonyl phenols with 0-5 units of ethylene oxide and/or propylene oxide (Empilan NP of Huntsmann), ethoxylated and/or propoxylated sorbitol with 5-20 units of ethylene oxide and/or propylene oxide (for example Armotan PN020 of ICI), fatty acids of coconut salified with K, MEA (Nansa of Huntsmann).
The main types of these surface-active agents are de-scribed in "Dispersing Powders in Liquids", Ralph D., Nel-son Jr., Ed. Elsevier, 1988.
The washing generally takes place at a temperature ranging from 20 to 50°C, in stirred containers containing the surface-active agent in a concentration ranging from 0.01 to 2% by weight, preferably from 0.02 to 1%.
At the end of the polymerization and washing with the surface-active agent, the beads produced are subjected to pre-treatment generally applied to traditional materials and which essentially consists in:
1. coating the beads with a liquid antistatic agent such as amines, tertiary ethoxylated alkylamines, ethylene ox-L5 ide-propylene oxide copolymers, etc. The purpose of this agent is to facilitate both the adhesion of the coating and also the screening of the beads prepared in suspen-sion;
2. applying the coating to the above beads, said coating essentially consisting of a mixture of mono-, di- and tri-esters of glycerin (or other alcohols) with fatty acids and of metallic stearates such as zinc and/or mag-nesium stearate.
Some illustrative but non-limiting examples are pro-?5 vided for a better understanding of the present invention and for its embodiment.
100 parts of styrene monomer, 0.30 parts of benzoyl peroxide, 0.15 parts of terbutylperbenzoate, 100 parts of demineralized water, 0.2 parts of tricalcium phosphate and 20 ppm of sodium dodecylbenzenesulfonate, were charged into a 2 litre reactor equipped with a stirrer.
The mixture was then heated to 90°C for 4 hours and to 125°C for a further 6 hours.
The expanding agent (7 parts of n-pentane) was added during the rise from 90 to 125°C.
At the end of the polymerization, the beads were cen-trifuged and subsequently washed with an equal part of de-mineralized water.
The beads were then centrifuged and placed in a column having a diameter of 10 cm and a height of 80 cm for drying with air at 23°C (flow-rate - 3, 000 1/h) . The time neces-sary for the drying was 40'.
0 . 02 0 of ethoxylated amine was added to the beads of expandable polymer thus produced, which were then sieved, separating the fraction with a diameter ranging from 1 to 1.5 mm.
0.250 of glycerylmonostearate and 0.05% of magnesium stearate were then added to the fraction.
The product is pre-expanded with vapour at a tempera-ture of 100°C at a density of 15 g/1 and then aged for a day.
The expanded beads were used the following day for the moulding of blocks (dimensions 1040 x 1030 x 550 mm) at a pressure of 0.5 bars, measuring the cooling time (which proved to be 12 minutes).
The blocks were then cut to prepare flat sheets on which the sintering was measured, which proved to be equal to 150.
50 g of the mother liquor of the polymerization and washing were put into a 200 g phial and stirred for a min-ute to evaluate the presence of foam. The formation of foam 1 cm high was observed, which completely disappeared after resting for 10 minutes.
The beads polymerized according to Comparative example 1 were centrifuged and then washed with an equal part of demineralized water containing 0.050 of sodium dodecylben-zenesulfonate.
The beads were then centrifuged and placed in a column having a diameter of 10 cm and a height of 80 cm for drying with air at 23°C (flow-rate - 3, 000 1/h) . The time neces-sary for the drying was 11 minutes.
The additive was added to the beads thus produced, which were sieved, expanded at 15 g/1, moulded according to the same procedure adopted in comparative example 1.
The cooling time proved to be 11 minutes whereas the sintering was equal to 50%.
50 g of the mother liquor of the polymerization and washing were put into a 200 g phial and stirred for a min ute to evaluate the presence of foam. The formation of per sistent foam, 10 cm high, was observed. The height of the foam was still 6 cm after resting for 10 minutes.
rmTw~nr ~
The beads polymerized according to Comparative example 1 were centrifuged and then washed with an equal part of demineralized water containing 0.05% of a non-ionic sur-face-active agent consisting of fatty alcohol condensed with ethylene oxide and propylene oxide, sold by Huntsman under the trade-name of Empilan 2638.
The beads were then centrifuged and placed in a column having a diameter of 10 cm and a height of 80 cm for drying with air at 23°C (flow-rate - 3,000 1/h). The time neces-sary for the drying was 10 minutes.
The additive was added to the beads thus prepared, which were sieved, etc., using the same procedure adopted in Comparative example l: the cooling time of the block proved to be 10 minutes whereas the sintering was equal to 50%.
50 g of the mother liquor of the polymerization and washing were put into a 200 g phial and stirred for a min-ute to evaluate the presence of foam. In this case no foam was present.
Claims (9)
1. A process for the preparation of expandable vinylaro-matic polymers which comprises:
a) polymerizing in aqueous suspension at last one vi-nylaromatic monomer in the presence of a suspending agent selected from inorganic salts of phosphoric acid;
b) recovering the expandable beads from the reaction con-tainer;
c) washing the beads thus obtained with an aqueous solu-tion containing 0.005-2% by weight of a non-ionic surface-active agent;
d) recovering the washed beads substantially without any inorganic salt of phosphoric acid, on the surface, and dry-ing them in a stream of air.
a) polymerizing in aqueous suspension at last one vi-nylaromatic monomer in the presence of a suspending agent selected from inorganic salts of phosphoric acid;
b) recovering the expandable beads from the reaction con-tainer;
c) washing the beads thus obtained with an aqueous solu-tion containing 0.005-2% by weight of a non-ionic surface-active agent;
d) recovering the washed beads substantially without any inorganic salt of phosphoric acid, on the surface, and dry-ing them in a stream of air.
2. The process according to claim 1, wherein the polym-erization in aqueous suspension of the vinylaromatic mono-mer is carried out in the presence of an initiator system and an expanding agent.
3. The process according to claim 2, wherein the initia-for system comprises two peroxides, one with a half time of an hour at 85-95°C and the other with a half time of an hour at 110-120°C.
4. The process according to claim 2, wherein the expand-ing agent capable of being englobed in the polymeric matrix consists of liquid substances with a boiling point ranging from 10 to 100°C.
5. The process according to any of the previous claims, wherein the expanding system is added in such quantities as to give a polymer in the form of beads which can be trans-formed to produce expanded articles having a density rang-ing from 5 to 50 g/l.
6. The process according to any of the previous claims, wherein the vinylaromatic monomer is selected from those having the general formula:
wherein n is zero or an integer ranging from 1 to 5, R is a hydrogen atom or a methyl and Y is a halogen, such as chlo-rine or bromine, or an alkyl or alkoxyl radical having from 1 to 4 carbon atoms.
wherein n is zero or an integer ranging from 1 to 5, R is a hydrogen atom or a methyl and Y is a halogen, such as chlo-rine or bromine, or an alkyl or alkoxyl radical having from 1 to 4 carbon atoms.
7. The process according to any of the previous claims, wherein the non-ionic surface-active agent is selected from alcohols/C8-C18 ethoxylated and/or propoxylated fatty acids, ethoxylated and/or propoxylated glycerin ethers with an av-erage molecular weight Mw ranging from 3500 to 5000, gly-cols condensed with ethylene oxide and/or propylene oxide, ethoxylated and/or propoxylated nonyl phenols with 0-5 units of ethylene oxide and/or propylene oxide, ethoxylated and/or propoxylated sorbitol with 5-20 units of ethylene oxide and/or propylene oxide, fatty acids of coconut sali-fled with K, MEA.
8. The process according to any of the previous claims, wherein the washing takes place at a temperature ranging from 20 to 50°C, in stirred containers containing the sur-face-active agent in a concentration ranging from 0.005 to 2% by weight, preferably from 0.02 to 10.
9. Expandable beads of vinylaromatic polymers obtainable according to the process of any of the previous claims com-prising 0.05-25% b.w. of athermaneous or refracting materi-als.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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ITMI2002A001448 | 2002-07-02 | ||
IT2002MI001448A ITMI20021448A1 (en) | 2002-07-02 | 2002-07-02 | PROCEDURE FOR THE PREPARATION OF VINYLAROMATIC POLYMERS |
PCT/EP2003/002866 WO2004005384A1 (en) | 2002-07-02 | 2003-03-19 | Process for the preparation of expandable vinylaromatic polymers |
Publications (2)
Publication Number | Publication Date |
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CA2489243A1 CA2489243A1 (en) | 2004-01-15 |
CA2489243C true CA2489243C (en) | 2010-08-10 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2489243A Expired - Fee Related CA2489243C (en) | 2002-07-02 | 2003-03-19 | Process for the preparation of expandable vinylaromatic polymers |
Country Status (15)
Country | Link |
---|---|
US (1) | US20050222357A1 (en) |
EP (1) | EP1525253B1 (en) |
JP (1) | JP4275068B2 (en) |
CN (1) | CN1281664C (en) |
AT (1) | ATE366276T1 (en) |
AU (1) | AU2003226663A1 (en) |
BR (1) | BR0312118B1 (en) |
CA (1) | CA2489243C (en) |
DE (1) | DE60314753T2 (en) |
ES (1) | ES2290499T3 (en) |
IT (1) | ITMI20021448A1 (en) |
MX (1) | MXPA04012684A (en) |
PL (1) | PL205615B1 (en) |
RU (1) | RU2299895C2 (en) |
WO (1) | WO2004005384A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITMI20071003A1 (en) | 2007-05-18 | 2008-11-19 | Polimeri Europa Spa | COMPOSITE BASED ON VINYLAROMATIC POLYMERS WITH IMPROVED PROPERTIES OF THERMAL INSULATION AND PROCEDURE FOR THEIR PREPARATION |
ITMI20080823A1 (en) * | 2008-05-07 | 2009-11-08 | Polimeri Europa Spa | COMPOSITIONS OF VINYLAROMATIC POLYMERS EXPANDABLE TO IMPROVED THERMAL INSULATION CAPACITY, PROCEDURE FOR THEIR PREPARATION AND ITEMS EXPANDED BY THEM |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4174427A (en) * | 1978-07-21 | 1979-11-13 | Basf Wyandotte Corporation | Method of making expandable polystyrene beads |
US4286069A (en) * | 1980-10-28 | 1981-08-25 | American Hoechst Corporation | Method of making expandable styrene-type beads |
US4692472A (en) * | 1986-05-05 | 1987-09-08 | Atlantic Richfield Company | Divinylbenzene in expandable beads for cup molding |
JP3878255B2 (en) * | 1996-10-17 | 2007-02-07 | 株式会社カネカ | Cleaning method of pre-expanded particles |
US6221926B1 (en) * | 1996-12-26 | 2001-04-24 | Kaneka Corporation | Expandable polystyrene resin beads, process for the preparation of them, and foam made by using the same |
DE19852678A1 (en) * | 1998-11-16 | 2000-05-18 | Basf Ag | Expandable styrene polymers containing graphite particles |
ITMI20012168A1 (en) * | 2001-10-18 | 2003-04-18 | Enichem Spa | EXPANDABLE VINYLAROMATIC POLYMERS AND PROCEDURE FOR THEIR PREPARATION |
-
2002
- 2002-07-02 IT IT2002MI001448A patent/ITMI20021448A1/en unknown
-
2003
- 2003-03-19 CA CA2489243A patent/CA2489243C/en not_active Expired - Fee Related
- 2003-03-19 DE DE60314753T patent/DE60314753T2/en not_active Expired - Lifetime
- 2003-03-19 AU AU2003226663A patent/AU2003226663A1/en not_active Abandoned
- 2003-03-19 US US10/516,935 patent/US20050222357A1/en not_active Abandoned
- 2003-03-19 EP EP03762476A patent/EP1525253B1/en not_active Expired - Lifetime
- 2003-03-19 JP JP2004518487A patent/JP4275068B2/en not_active Expired - Fee Related
- 2003-03-19 ES ES03762476T patent/ES2290499T3/en not_active Expired - Lifetime
- 2003-03-19 MX MXPA04012684A patent/MXPA04012684A/en active IP Right Grant
- 2003-03-19 AT AT03762476T patent/ATE366276T1/en not_active IP Right Cessation
- 2003-03-19 RU RU2004137277/04A patent/RU2299895C2/en not_active IP Right Cessation
- 2003-03-19 PL PL373217A patent/PL205615B1/en unknown
- 2003-03-19 WO PCT/EP2003/002866 patent/WO2004005384A1/en active IP Right Grant
- 2003-03-19 BR BRPI0312118-6A patent/BR0312118B1/en not_active IP Right Cessation
- 2003-03-19 CN CN03815556.7A patent/CN1281664C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP1525253B1 (en) | 2007-07-04 |
ATE366276T1 (en) | 2007-07-15 |
WO2004005384A1 (en) | 2004-01-15 |
US20050222357A1 (en) | 2005-10-06 |
RU2299895C2 (en) | 2007-05-27 |
BR0312118A (en) | 2005-03-29 |
CN1665867A (en) | 2005-09-07 |
JP4275068B2 (en) | 2009-06-10 |
ITMI20021448A0 (en) | 2002-07-02 |
CA2489243A1 (en) | 2004-01-15 |
RU2004137277A (en) | 2005-08-10 |
DE60314753D1 (en) | 2007-08-16 |
CN1281664C (en) | 2006-10-25 |
MXPA04012684A (en) | 2005-03-23 |
BR0312118B1 (en) | 2012-12-11 |
PL373217A1 (en) | 2005-08-22 |
AU2003226663A1 (en) | 2004-01-23 |
ES2290499T3 (en) | 2008-02-16 |
PL205615B1 (en) | 2010-05-31 |
JP2005531674A (en) | 2005-10-20 |
DE60314753T2 (en) | 2008-07-24 |
EP1525253A1 (en) | 2005-04-27 |
ITMI20021448A1 (en) | 2004-01-02 |
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Effective date: 20160321 |